In asymmetric reduction, asymmetric isomerization and the like using a transition metal coordinated with optically active phosphine as a catalyst, 2,2′-(bis(diphenylphosphino)-1,1′-binaphthyl (hereinafter sometimes to be abbreviated as BINAP) is generally used as the optically active phosphine. Depending on the kind of substrate, however, reactivity, stereoselectivity, catalytic efficiency and the like are insufficient. Therefore, various optically active phosphines have been produced and reported (e.g., Handbook of Enantioselective Catalysis with Transition Metal Compounds, VCH Publishers (1993)). For example, JP-A-S63-63690 teaches that a ruthenium complex using 2,2′-bis(di(p-toluoyl)phosphino)-1,1′-binaphthyl as a ligand is useful for the asymmetric reduction of a carbon-carbon double bond, JP-A-H3-255090 teaches that a ruthenium complex using 2,2′-bis(di(3,5-dialkylphenyl)phosphino)-1,1′-binaphthyl as a ligand is useful for the asymmetric reduction of β-keto ester.
As the production methods of BINAP and BINAP analogs,    1) JP-A-H3-255090 describes the following reaction formula as a production method of a compound represented by the formula
wherein R is a lower alkyl group (hereinafter to be abbreviated as 3,5-DABIN):

As regards the above-mentioned optical resolution, this reference describes as follows. That is, racemic compound (IX) is dissolved by heating in carbon tetrachloride, a solution of (−)-benzoyltartaric acid in ether is added and the mixture is stirred. The crystals are precipitated, and the crystals are repeatedly recrystallized until they show a certain level of rotation. The purified crystals are suspended in methylene chloride, and 2N sodium hydroxide is added, whereby free phosphine oxide (−)-(IX) in a (−) form is obtained.    2) JP-T-H10-501234 or WO 95/32934 describes a production method of BINAP, which comprises reacting a compound represented by the formula
wherein R is triflate, mesylate or tosylate, with diphenylphosphine in the presence of an amine base and a nickel catalyst.    3) JP-A-H9-124669 describes a production method of optically active diphosphine represented by the formula
wherein A is a phenyl group, a substituted phenyl group, a naphthyl group optionally substituted by a lower alkyl group or a lower alkoxy group, which comprises reacting an optically active 2,2′-bis(trifluoromethanesulfonyloxy)-1,1′-binaphthyl with phosphine oxide represented by the formula A2P(O)H wherein A is as defined above, in the presence of a transition metal-phosphine complex to synthesize a mixture containing an optically active diphosphine compound and/or an optically active diphosphine monoxide compound, and further reacting the mixture containing the optically active diphosphine compound and/or the optically active diphosphine monoxide compound with a reducing agent.    4) Chemical Communications, pp. 2359-2360 (1997) describes a production method to give (S)-BINAP, which comprises reacting (S)-2,2′-bis(trifluoromethanesulfonyloxy)-1,1′-binaphthyl with diphenylphosphine chloride in the presence of NiCl2.[1,2-bis(diphenylphosphino)ethane] and zinc.    5) JP-A-2000-7688 describes a production method of optically active 2,2′-bis(di-substituted phosphino)-1,1′-binaphthyl, which comprises reacting a sulfonic acid ester of optically active 2,2′-dihydroxy-1,1′-binaphthyl represented by the formula
wherein R1 is an alkyl group, a perfluoroalkyl group, an aryl group or a perfluoroaryl group, with chloro di-substituted phosphine represented by the formula
wherein R2 and R3 may be the same or different and each is an aryl group or a cycloalkyl group, in the presence of a hydrogen, an amine, a hydrogenation catalyst and a transition metal catalyst.    6) JP-A-2000-136194 describes a production method of a compound represented by the formula
wherein ring A, ring B, ring C and ring D are each a benzene ring having a substituent, which comprises reacting a compound represented by the formula
wherein R1 and R2 are each an optionally substituted alkylsulfonyl group or an optionally substituted arylsulfonyl group, with diphenylphosphine having a substituent, in the presence of an amine and a transition metal.
As a phosphine-borane complex,    7) Tetrahedron Letters, vol. 40, pp. 201-204 (1999) describes a production method to give a monophosphine compound by reacting aryl triflate or aryl nonaflate with a diphenylphosphine-borane complex in the presence of a transition metal and a base.    8) Tetrahedron Asymmetry, vol. 5, pp. 325-328 (1994) describes that synthesis of a diphosphine compound by reacting 2,2′-dimethoxy-7,7′-bis(trifluoromethanesulfonyloxy)-1,1′-binaphthyl with a diphenylphosphine-borane complex in the presence of a transition metal did not succeed.    9) As regards a diphenylphosphine-borane complex wherein a phenyl group has a substituent, U.S. Pat. No. 2,926,194 describes a bis(p-methylphenyl)phosphine-borane complex, a bis(p-biphenylyl)phosphine-borane complex and a bis(2-naphthyl)phosphine-borane complex, and Tetrahedron, vol. 51, pp. 7655-7666 (1995) describes a bis(4-methoxy-2-methylphenyl)phosphine-borane complex.
In the aforementioned 2), 4), 5) and 6), a trivalent organic phosphorus compound which is susceptible to oxidization and unstable is used as a reaction reagent, and in the aforementioned 1) and 3), trichlorosilane is used as a reducing agent. Therefore, they are not industrially advantageous methods, and establishment of a production method of BINAP and BINAP analogs, which is suitable for industrial mass production, has been desired.
On the other hand, in the aforementioned 7) and 8), reaction of a diphenylphosphine-borane complex, which is stable and easy to handle, with aryl triflate was tried. In 7), synthesis of a monophosphine compound alone was successful but as described in 8), synthesis of a diphosphine compound necessary for the production method of BINAP was not successful.
For synthesis of various BINAP analogs from a diphenylphosphine-borane complex, a diphenylphosphine-borane complex comprising a phenyl group having a substituent is necessary. However, in 9), synthesis examples of only 4 kinds of diphenylphosphine-borane complexes are merely described.